2,3-dialkyl-n((haloalkyl)thio)bicarbamimides



United States Patent O 3,484,451 2,3-DIALKYL-N[(HALOALKYL)THIO]BICARBAMIMIDES Malcolm W. Moon, Kalamazoo, Mich., assignor to The UpjohnCompany, Kalamazoo, Mich., a corporation of Delaware No Drawing. FiledApr. 14, 1967, Ser. No. 630,827 Int. Cl. C07d 55/10; A01n 9/22 U.S. Cl.260308 6 Claims ABSTRACT OF THE DISCLOSURE Certain new2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimides are active against fungiand bacteria. Alkyl groups of from 1 to 12 carbon atoms are disclosed;and haloalkyl groups on the imide nitrogen having 1 and 2 carbon atoms,and the halogens chlorine, bromine, and fluorine are disclosed. Thecompounds can be used against bean root rot fungi.

SUMMARY OF THE INVENTION II /C R N N-S-haloalkyl R -N wherein R and Rare alkyl of from 1 to 12 carbon atoms, inclusive, and haloalkyl is l or2 carbon atoms with at least 2, preferably 3 or 4, halogen atoms.

Examples of alkyl of from 1 to 12 carbon atoms, inclusive, are methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl and dodecyl, including isomeric forms thereof. Examples ofhaloalkyl of 1 or 2 carbon atoms are trichloromethyl,bromochlorofluorornethyl, bromodichloromethyl, chlorodifluoromethyl,fiuorodichloromethyl, 2,2,2-trichloroethyl, 1,2,2- trichloroethyl,dichloromethyl, 1,1,2,2-tetrachloroethyl, and the like.

It has been found that the new2,3-clialkyl-N-[(haloalkyl)thio]bicarbamimides of this invention areactive against microorganisms. The compounds are particularly activeagainst fungi and bacteria. Illustratively, the bean root rot fungi,Fusarium solani f. Phaseoli and Rhizoct-onia solani, are controlled by2,3-dimethyl-N-[(trichloromethyl)thioJbicarbamimide. The compOund isalso active against the fungi Botrytis cinerea, Fusarz'um oxysp-orum,Monolinia fructicola, Pythium ultimum, Stemphyllium species,Verticillium albo-atrum, and Cytospora species. The compound is activeagainst bacteria, for example, Psudomonas phaseolicola and Xanthomonasvesicatoria. The compounds of this invention can be used, therefore, tocontrol both bacteria and fungi.

In accordance with the invention, the novel 2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimides can be used in the novel compositionsof the invention to control fungal and bacterial growth on organicmatter such as wood, cellulosic fibers, seeds, fruits, and vegetables;living plants; soil;

"ice

and on animals such as fish, reptiles, birds, cattle, horses, dogs,cats, and other animals. The invention includes, therefore, newcompounds, new compositions, and a new method for controlling fungi andbacteria in general as well as specific fungi and bacteria that arepathogenic to seeds, plants, and animals.

DETAILED DESCRIPTION The new 2,3 dialkyl N[(haloalkyl)thio1bicarbamimides of this invention (compounds ofFormula 1) are prepared by reacting a haloalkylsulfenyl halide,preferably a chloride, with an alkali metal salt of a2,3-dialkylbicarbamimide. The reaction is advantageously efiecte-d in anaqueous medium, preferably an aqueous solution of an alkali metalhydroxide (e.g., sodium or potassium hydroxide) so as to form the alkalimetal salt of the bicarbamimide in situ. A pre-formed alkali metal saltof a bicarbamimide can be used if desired. Heat is evolved by thereaction of the alkali metal-irnide salt and the haloalkylsulfenylhalide, so the reactants should be mixed slowly accompanied by thoroughstirring. The temperature of thereaction mixture is conveniently kept atabout 0 C., but reaction temperatures as low as about 10 C. and as highas about 30 C. can be used. At the higher temperatures the reactantsshould be mixed more slowly. The reaction product separates from thereaction mixture as a solid or can be precipitated by the addition oforganic media. for example, petroleum ether (preferably), acetone,benzene, and the like.

The stoichiometry of the reaction requires one molecular equivalent ofthe haloalkylsulfenyl for each molecular equivalent of thebicarbamimide. In general, however, a slight excess of thehaloalkylsulfenyl halide is preferred, although an excess of eitherreactant can be used if desired.

The new 2,3 dialkyl-N-[(haloalkyl)thio]bicarbamimides are recovered fromthe reaction mixture and purified by conventional methods. When thedesired product separates as a solid from the reaction mixture, it canbe recovered on a filter, washed free of by-products and unreactedstarting materials, and purified by recrystallization from a suitableliquid medium, e.g., petroleum ether, benzene, and acetone, and thelike.

Alternatively, the compounds of Formula 1 can be prepared by suspendingan anhydrous alkali metal salt of a 2,3-dialkylbicarbamimide in an inertreaction medium, e.g., benzene, toluene and the like, and heating toabout 50 -80 C. in the presence of a selected haloalkylsulfenyl halide.After the reaction is completed the reaction mixture is cooled andfiltered, and the filtrate is concentrated in order to obtain thedesired compound.

The starting 2,3 dialkylbicarbamimides are preparable according to knownmethods. Illustratively, they can be prepared by heating and cyclizing a1,2-dialkyl-1,2-dicarbamylhydrazine. The cyclization is effected byheating the 1,2-dialkyl-1,2-dicarbamylhydrazine at a temperature ofabout 250 C. according to the method of Arndt et al., Rev. facult sci.univ. Istanbul 13A, pp. 127-146 (1948) [C.A. 42, p. 8190 (1948)].

The starting 1,2-dialkyl-1,2,dicarbamylhydrazines are prepared bycondensing a 1,2-dialkylhydrazine acid addition salt with potassiumcyanate. Two molecular equivalents of the potassium cyanate permolecular equivalent of the 1,2-dialkylhydrazine salt are requiredaccording to stoichiometric theory.

Some representative known 1,2-dialkylhydrazines for the synthesisinclude 1,2dimethylhydrazine, 1,2-diethylhydrazine, 1,2dipropylhydrazine, 1,2 diisopropylhydrazine, 1,2 diisobutylhydrazine,and l-methyl 2-isopropylhydrazine. Other representative 1,2dialkylhydrazines can be prepared according to known methods,

3 e.g., th method described by Renaud and Leitch, Can. J. Chem. 32, p.545 (1954).

Alternatively, the starting 2,3-dialkylbicarbamimides are prepared byalkylating a 2-alkylbicarbamimide. Illustratively, Arndt et al., supra,prepared 2-methylbicarbamimide by condensing 2-m'ethylsemicarbazide withethyl chlorocarbonate by heating at the reflux temperature in ethylacetate to obtain l-carbethoxy-Z-rnethylsemicarbazide which when boiledin aqueous 2 N NaOH and neutralized with acid gave2-methylbicarbamimide. The 2-alkylbicarbamimides prepared in this waycan be alkylated by conventional procedures to give symmetrical orunsymmetrical 2,3-dialkylbicarbamimides.

Alternatively, the 2,3 dialkylbicarbamimides can be prepared by theprocedure described in US. Patent No. 2,944,060.

The novel 2,3 dialkyl N [(haloalkyl)thio]bicarbamimides of thisinvention (compounds according to Formula 1) are formulated asfungicides and bactericides with solid and liquid carriers with orwithout adjuvants. The compounds can be used in pure form, but generallythe interest of economy is best served by the formulations of theinvention. The pure active compounds or the formulations can be appliedto fungi, bacteria, objects, or situs for preventing fungal andbacterial growths. The microbiocidal formulations of this inventioninclude dispersions in powder and granular carriers, e.g., dusts andgranules; dispersions in liquid carriers, e.g., true solutions,suspensions and emulsifiable concentrates; smokes and aerosols;emulsions, i.e., creams and ointments; and capsules and tablets.

The 2,3 dialkyl N [(haloalkyl)thio]bicarbamimides of this invention aresolids, and they can be readily formulated as dusts by grinding amixture of the compound and a pulverulent carrier in the presence ofeach other. Grinding is conveniently accomplished in a ball mill, ahammer mill, or by air-blast micronization. A suitable ultimate particlesize is less than 60 microns. Preferably, 95% of the particles are lessthan 50 microns, and about 75% are 5 to 20 microns. Dusts of that degreeof comminution are conveniently free-flowing and can be applied toanimals, inanimate matter, fruit trees, crop plants, and soil so as toeffect thorough distribution and coverage. Dusts are particularlyadapted for effectively controlling plant fungi over wide areas whenapplied by airplane. They are also indicated for application to theundersides of plant foliage and to the skin of hairy animals.

Representative suitable pulverlent carriers include the natural clayssuch as China, Georgia, Barden, attapulgus, kaolin, and bentonite clays;minerals in their natural forms as they are obtained from the earth suchas talc, pyrophyllite, quartz, diatomaceous earth, fullers earth, chalk,rock phosphates and sulfates, calcium carbonates, sulfur, silica andsilicates; chemically modified minerals such as washed bentonite,precipitated calcium phosphate, precipitated calcium carbonate,precipitated calcium silicate, synthetic magnesium silicate, andcolloidal silica; and organic flours such as wood, Walnut shell,soybean, cottonseed, and tobacco flours, and free-flowing, hydrophobicstarches.

Dusts can also be prepared by dissolving the 2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimides in a volatile solvent such asmethylene chloride, mixing the solution with a pulverulent carrier andevaporating the solvent.

The proportions of pulverlent carrier and 2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimide can vary over a wide range dependingupon the microbes to be controlled and the conditions of treatment. Ingeneral, dust formulations can contain up to about 90% (on a weightbasis) of the active ingredient. Dusts having as little as 0.001% of theactive ingredient can be used, but a generally preferred proportion isfrom about 0.50% to about 20% of active ingredient.

The dispersible powder formulations of this invention are prepared byincorporating a surfactant in a dust composition prepared as describedabove. When about 0.1% to about 12% of a surfactant is incorporated in adust, the dispersible powder thus obtained is particularly adapted forfurther admixture with water for spraying on inanimate matter andproducts, fruit trees, field crops, soil, and livestock. The dispersiblepowders can be admixed with water to obtain any desired concentration ofactive ingredient, and the mixture can be applied in amounts sufiicientto obtain predetermined rates of application and uniform distribution.With this flexibility in mind, the dispersible powders of the inventioncan conveniently comprise preferably about 10% to about of activeingredient.

Representative surfactants useful for preparing dispersible powderformulations of this invention include alkyl sulfates and sulfonates,alkyl aryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfates,polyoxyethylenesorbitan monolaurate, alkyl aryl polyether sulfates,alkyl aryl polyether alcohols, alkyl naphthalene sulfonates, alkylquaternary ammonium salts, sulfated fatty acids and esters, sulfatedfatty acid amides, glycerol mannitan laurate, polyalkylether condensatesof fatty acids, lignin sulfonates, and the like. The preferred class ofsurfactants includes blends of sulfonated oils and polyalcoholcarboxylic acid esters (Emcol H-77), blends of polyoxyethylene ethersand oil-soluble sulfonates (Emcol H- 400), blends of alkyl arylsulfonates and alkylphenoxy polyethoxy ethanols (Tritons X-151, X161,and X-l71), e.g., about equal parts of sodium kerylbenzene sulfonate andisooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups,and blends of calcium alkyl aryl sulfonates and polyethoxylatedvegetable oils (Agrimul N 8). It will be understood, of course, that thesulfate and sulfonate surfactants suggested above will preferably beused in the form of their soluble salts, for example, their sodiumsalts. All of these surfactants are capable of reducing the surfacetension of water to less than about 40 dynes per centimeter inconcentrations of about 1% or less. The dispersible powder compositionscan be formulated with a mixture of surfactants of the types indicatedif desired.

A suitable dispersible powder formulation is obtained by blending andmilling 327 lbs. of Georgia clay, 4.5 lbs. of isooctylphenoxy polyethoxyethanol (Triton X-l00) as a wetting agent, 9 lbs. of a polymerizedsodium salt of substituted benzoid long-chain sulfonic acid (DaXad 27)as a dispersing agent, and 113 lbs. of the active ingredient. Theresulting formulation has the following percentage composition (partsherein are by weight unless otherwise specified):

Percent Active ingredient 25 Isooctylphenoxy polyethoxy ethanol 1Polymerized sodium salt of substituted benzoid longchain sulfonic acid 2Georgia clay 72 This formulation, when dispersed in water at the rate of10 lbs. per gals, gives a spray formulation containing about 0.3% (3000ppm.) active ingredient which can be applied to soil, plant growthmedia, or turf at the rate of 40 gals. per acre to give a totalapplication of active ingredient of 1 lb. per acre.

If desired, dispersants such as methyl cellulose, polyvinyl alcohol,sodium ligninsulfonates, and the like can be included in the dispersiblepowder formulations of this invention. Adhesive or sticking agents suchas vegetable oils, naturally occurring gums, casein, and others can alsobe included. Corrosion inhibitors such as epichlorohydrin andanti-foaming agents such as stearic acid can also be included.

The granular formulations according ot this invention are prepared bypermeating a granular carrier with a solution of a2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimide and then drying thegranules. Suitable granular carriers include vermiculite, pyrophyllite,and attapulgite. Suitable solvents include acetone, methyl ethyl ketone,and methylene chloride. A solution of a 2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimide is sprayed on a granular carrier while the carrier isbeing mixed and tumbled. The granules are then dried. The granules canrange in size from about to about 60 mesh, preferably about 30 to about60 mesh.

The compounds of this invention can be applied to fungi, bacteria,objects, or situs in aqueous sprays without a solid carrier. Since,however, the compounds themselves are relatively insoluble in water theyare preferably dissolved in a suitable inert organic solvent carrier.Advantageously, the solvent carrier is immiscible with water so that anemulsion of the solvent carrier in Water can be prepared. If, forexample, a Water-miscible solvent carrier such as ethanol is used thesolvent carrier will dissolve in the water and any excess compound willbe thrown out of solution. In an oil-in-water emulsion, the solventphase is dispersed in the water phase and the dispersed phase containsthe active ingredient. In this way, uniform distribution of a waterinsoluble active ingredient is achieved in an aqueous spray. A solventcarrier in which 2,3-dialkyl-N-[(haloalkyl)thio]bicarbamimides arehighly soluble is desirable so that relatively high concentrations ofactive ingredient can be obtained. Sometimes, one or more solventcarriers with or without a cosolvent can be used in order to obtainconcentrated solutions of the active ingredient, the main considerationbeing to employ a water-immiscible solvent for the active ingredientthat will hold the compound in solution over the range of concentrationsuseful for preventing fungal and bacterial growths.

The emulsifiable concentrates of the invention are prepared, therefore,by dissolving the active ingredient and a surfactant in a substantiallywater-immiscible solvent carrier (i.e., a solvent carrier which issoluble in water to the extent of less than 2.5% by volume attemperatures of the order of to 30 C.), for example, cyclohexanone,methyl propyl ketone, summer oils, ethylene dichloride, aromatichydrocarbons such as benzene, toluene, and xylene, and high-boilingpetroleum hydrocarbons such as kerosene, diesel oil, and the like. Ifdesired, a cosolvent such as methyl ethyl ketone, acetone, isopropanol,and the like can be included with the solvent carrier in order toenhance the solubility of the active ingredient. Aqueous emulsions arethen prepared by mixing with water to give any desired concentration ofactive ingredient. The surfactants which can be employed in the aqueousemulsions of the invention are those types noted above. Mixtures ofsurfactants can be employed, if desired.

Advantageously, the concentration of active ingredient in theemulsifiable concentrates can range from about 5% to about 50% byweight, preferably from about 10% to about 40%. A concentrate comprising20% (by weight) of the compound dissolved in a water-immiscible solventof the kind noted above can be admixed with an aqueous medium in theproportions of 13 ml. of concentrate with 1 gal. of medium to give amixture containing 700 parts of active ingredient per million parts ofliquid carrier. Similarly, 1 qt. of a 20% concentrate mixed with 40gals. of water provides about 1200 ppm. (parts per million) of activeingredient. In the same manner, more concentrated solutionsof activeingredient can be prepared.

The concentrate compositions of the invention which are intended for usein the form of aqueous dispersions or emulsions can also comprise ahumectant, that is to say, an agent which will delay the drying of thecomposi' tion in contact with material to which it has been applied.Suitable humectants include glycerol, diethylene glycol, solubilizedlignins, such as calcium ligninsulfonate, and the like.

The rates of application to fungi, bacteria, objects, or situs willdepend upon the species of microbes to be controlled, the presence orabsence of desirable living organisms, temperature conditions oftreatment, and the method and efficiency of application. In general,fungicidal activity is obtained when the compounds are applied atconcentrations of about 10 to about 6000 p.p.m., preferably atconcentrations of about to about 1200 ppm.

The compositions containing2,3-dialky1-N-[(haloalkyl)thio]bicarbamimides according to theinvention, can be applied by conventional methods to fungi, bacteria,objects or any situs where control of fungi and bacteria is desired. Forexample, an area of soil or plants can be treated by spraying wettablepowder suspensions, emulsions, or solutions from boom-type powersprayers or from hand-operated knapsack sprayers. Dusts can be appliedby power dusters, or by hand-operated dusters, Creams and ointmentformulations can be applied to skin or objects for prolonged protectionfrom fungi and bacteria.

The following examples are illustrative of the process and products ofthe present invention, [but are not to be construed as limiting.

EXAMPLE 1 Preparation of 2,3-dimethyl-N- (trichloromethyl thio]bicarbumimide Trichloromethylsulfenyl chloride (3.0 ml.) was addeddropwise with stirring to a chilled solution of 2,3-dimethylcarbamimide(3.15 gm., 0.024 mole) in aqueous sodium hydroxide (prepared bydissolving 0.98 gm. sodium hydroxide in 20 ml. water). The precipitatethat formed was collected on a filter; and the filter cake was washedwith water and petroleum ether. After drying and recrystallizing from amixture of benzene and petroleum ether, there was obtained2,3-dimethyl-N- [(trichloromethyl)-thio]bicarbamimide having a meltingpoint of 81 to 83 C.

Analysis.Calcd for C H Cl N O S: C, 21.56; H, 2.17; Cl, 38.19; N, 15.09;S, 11.51. Found: C, 21.79; H, 2.37; Cl, 38.34; N, 15.15; S, 11.24.

Following the same procedure, but substitutingfluorodichloromethylsulfenyl chloride, dichloromethylsulfenyl chloride,2,2,2 trichloroethylsulfenyl chloride, 1,2,2- trichloroethylsulfenylchloride, 1,1,2,2-tetrachloroethylsulfenyl chloride,bromochlorofiuoromethylsulfenyl chloride, bromodichloromethylsulfenylchloride, and chlorodifluoromethylsulfenyl chloride, respectively, fortrichloromethylsulfenyl chloride there are prepared:

2, 3-dimethyl-N-[ (fiuorodichloromethyl) thio] bicarbamimide,

2, 3-dimethyl-N-[ (dichloromethyl) thio] bicarbamimide,

2, 3-dimethyl-N- (2,2,2-trichloroethyl) thio] bicarbamimide,

2, 3-dimethyl-N-[ l ,2,2-trichloroethyl) thio] bicarbamimide,

2, 3-dimethyl-N- 1,1,2,2-tetrachloroethyl)thi0]bicarbamimide,

2, 3-dimethyl-N- (bromochlorofluoromethyl) thio] bicarb amimide,

2,3-dimethyl-N-[ (bromodichloromethyl) thio] bicarbamimide, and

2, 3 -dimethyl-N-[ (chlorodifluoromethyl) thio] bi carbamimide,respectively.

EXAMPLE 2 Preparation of 2,3-diis0propyZ-N-[(trichloromethyl)-thi01bicarbamim ide Trichloromethylsulfenyl chloride (4.0 ml.) was addeddropwise with stirring to a chilled solution of2,3-diisopropylbicarbamimide (4.0 gm., 0.022 mole) in 22.0 ml. 1 Naqueous sodium hydroxide. After diluting the reaction mixture with 10ml. cold petroleum ether, stirring was continued at 0 C. for 30 min. Theprecipitate that formed was collected on a filter; and the filter cake 7was washed -with water and dried. The dry filter cake was recrystallizedfrom a mixture of acetone and petroleum ether, and then from a mixtureof benzene and petroleum ether. There was thus obtained 2,3-diisopropyl-N-[(trichloromethyl)thio]bicarbamimide having a melting point of 83 to88 C.

Analysis.Calcd for C H Cl N O S: N, 12.56; S, 9.59. Found: N, 12.75; S,9.42.

EXAMPLE 3 Preparation 2,3-dipr0pyl-N-[ (tric/zloromellzyl) thio]bicarbamimide Trichloromethylsulfenyl chloride (3.0 ml.) was addeddropwise with stirring to a chilled solution of1,2-dipropylbicarbamimide (2.5 gm., 0.014 mole) in 13.5 ml. 1 N aqueoussodium hydroxide. After diluting the reaction mixture with 15 ml. coldpetroleum ether, stirring was continued at 0 C. for min. The precipitatethat formed was collected on a filter; and the filter cake Was dried.After recrystallizing from petroleum ether, there Was obtained2,3-dipropyl-N-[(trichloromethyl) thio]-bicarbamimide having a meltingpoint of 85 to 87 C.

Analysis.Calcd for C H Cl N O S: C, 32.30; H, 4.22; Cl, 31.79; N, 12.56;S, 9.59. Found: C, 32.51; H, 4.35; Cl, 31.80; N, 12.68; S, 9.59.

EXAMPLE 4- Following the procedure of Example 2, but substituting 2,3diethylbicarbamimide, 2,3 di sec butylbicarbamimide, 2,3diisobutylbicarbamimide, and 2 ethyl-3- isopropylbicarbamimide for 2,3diisopropylbicarbamimide, there are prepared 2,3diethyl-N-[(trichloromethyl)thio]bicarbamimide, 2,3 di secbutyl-N[(trichloromethyl)thio]bicarbamimide, 2,3 -diisobutyl N-[(trichloromethyl)thioJbicarbamimide, and 2 ethyl-3- isopropyl N[(trichloromethyl)thio]bicarbamide, respectively.

Further following the same procedure but substituting the indicatedbicarbamimides, 2-methyl-3-ethylbicarbarrlimide, 2 methyl 3propylbicarbamimide, 2 methyl- 3 isopropylbicarbamimide, 2 methyl 3neopentylbicarbamimide, 2 methyl 3 hexylbicarbamimide, 2- methyl 3octylbicarbamimide, 2-methyl3dodecylbicarbamimide, 2 methyl 3 secbutylbicarbamimide, 2 methyl 3 heptylbicarbamimide, and 2 methyl-3-butylbicarbamimide for the 2,3-diisopropylbicarbamirnide there can beprepared:

2-methyl-3-ethyl-N-[ (trichloromethyl) thio]bicarbamimide,

2-methyl-3-propyl-N-[ (trichloromethyl) thio bicarbamimide,

2-methyl-3-isopropyl-N- (trichloromethyl thio bicarbamimide,

2-methyl-3-neopentyl-N-[(trichloromethy1)thio]bicarbamimide,

2-methyl-3-hexyl-N- (trichloromethyl) thio bicarbamimide,

2-methyl-3-octyl-N- trichloromethyl)thio] bicarbamimide,

2-methyl-3-dodecyl-N-[ (trichloromethyl thio] bicarbamimide,

2-methyl-3-sec-butyl-N-[ (trichloromethyl thio] bicarbamimide,

2-methyl-3-heptyl-N-[ (trichloromethyl) thio] bicarbamimide, and

2-methyl-3-butyl-N-L (trichloromethyl thio] bicarbamimide, respectively.

I claim: 1. The 2,3-dialkyl-N- (haloalkyl) thio] bicarbamimides of theformula:

wherein R and R are alkyl 01 from 1. to 12 carbon atoms, inclusive, andhaloalkyl has 1 or 2 carbon atoms with at least 2 halogen atomsubstituents.

2. The compound according to claim 1 wherein haloalkyl is trihalomethyl.

3. The compound according to claim 2 wherein trihalomethyl istrichloromethyl.

4. 2,3-dimethyl N-[(trichloromethyl)thio]bicarbamimide according toclaim 3.

5. 2,3 diisopropyl N (trichloromethyl)thio] bicarbamimide according toclaim 3.

6. 2,3-dipropyl N [(trichloromethyl)thio]bicarbamimide according toclaim 3.

No references cited.

ALTON D. ROLLINS, Primary Examiner U.S. Cl. X.R.

